The aluminophosphate (AlPO) JDF-2 is prepared hydrothermally with methylammonium hydroxide (MAH·HO, MAH = CHNH), giving rise to a microporous AEN-type framework with occluded MAH cations and extra-framework (Al-bound) HO anions. Despite the presence of these species within its pores, JDF-2 can hydrate upon exposure to atmospheric moisture to give AlPO-53(A), an isostructural material whose crystal structure contains one molecule of HO per formula unit. This hydration can be reversed by mild heating (such as the frictional heating from magic angle spinning). Previous work has shown good agreement between the NMR parameters obtained experimentally and those calculated from the (optimized) crystal structure of JDF-2. However, several discrepancies are apparent between the experimental NMR parameters for AlPO-53(A) and those calculated from the (optimized) crystal structure (e.g. four C resonances are observed, rather than the expected two). The unexpected resonances appear and disappear reversibly with the respective addition and removal of HO, so clearly arise from AlPO-53(A). We investigate the ambient hydration of JDF-2 using quantitative P MAS NMR to follow the transformation over the course of ∼3 months. The structures of JDF-2 and AlPO-53(A) are also investigated using a combination of multinuclear solid-state NMR spectroscopy to characterize the samples, and first-principles density functional theory (DFT) calculations to evaluate a range of possible structural models in terms of calculated NMR parameters and energetics. The published structure of JDF-2 is shown to be a good representation of the dehydrated material, but modification of the published structure of AlPO-53(A) is required to provide calculated NMR parameters that are in better agreement with experiment. This modification includes reorientation of all the MAH cations and partial occupancy of the HO sites.